Polymerization of cis type ii olefins



United States Patent Ofifice 3,341,619 Patented Sept. 12, 1967 3,341,619 PDLYMERIZATION F CIS TYPE 11 OLEFINS Eugene L. Stogryn, Fords, N.J., and Herbert F. Strobmayer, Wezembeek-Ophem, Brabant, Belgium, assignors to Esso Research and Engineering Company, a corporation of Delaware No Drawing. Filed Apr. 13, 1964, Ser. No. 359,416 7 Claims. (Cl. 260-68345) This invention relates to the preparation of polymers of the cis isomer of Type II olefins and more particularly relates to the homopolymerization and copolymerization of the above olefins with a catalyst formed by the activation of a reducible transition metal compound with an organo-metallic compound.

The low pressure polymerization and copolymerization of alpha olefins with catalyst systems made up of a partially reduced heavy transition metal halide and a reducing metal containing compound is well known. See, e.g., Belgian Patent 533,362, Chemical and Engineering News, Apr. 8, 1957, pages 12 through 16, and Petroleum Refiner, Dec. 1956, pages 191 through 196.

However, heretofore the polymerization of internal olefins, i.e., Type II olefins, has not been successfully accomplished by the use of catalysts of the above type. Dr. G. Natta, one of the foremost authorities on olefin polymerization with Ziegler-type catalyst, stated in a letter to the editor of the Journal of the American Chemical Society, vol. 83 (1961), pages 3343 and 3344, that with all the catalysts of the anionic coordinated type used by us no homopolymerization of butene-2 occurs.

It has now been found surprisingly that the cis isomer of C C Type II olefins can be successfully polymerized using as catalyst a transition metal compound of Groups IVA, V-A, VI-A, VII-A, and VIII activated with an organo-metallic compound of Groups I-A and II-A of the Periodic Table.

The olefins polymerized by the present invention are cis isomers of C C preferably 0., to C Type II olefins. By Type II olefin is meant an olefin having one hydrocarbon group on each of the carbon atoms containing the olefin double bond: See Science of Petroleum, vol. II, page 1349 (1938), by C. E. Boord. The hydrocarbon groups attached to the carbon atoms containing the olefin double bond can be straight or branched chain and are acyclic, alicyclic, or aralkyl. Examples of the olefins polymerized by the invention are cis Z-butene, cis 2- pentene, cis Z-hexene, cis 3-hexene, cis 4-methyl 2- pentene, cyclopentene, cyclohexene, cis l-phenyl Z-butene, etc.

The low pressure polymerization catalysts useful for the present invention are reducible transition metal compounds of Groups IV-A, V-A, VI-A, VIIA and VIII of the Periodic System activated with from 0.5 to 10 moles, preferably 1 to 3 moles, of an organo-metallic compound of a metal of the A sub-group of Groups I and II of the 1956, page 313) per mole of transition metal compound. The reducible transition metal compounds which can be used include inorganic compounds such as the halides, oxyhalides, complex halides and organic compounds such as alcoholates, acetates, benzoates and acetyl acetonates. The metal halides, particularly the chlorides, are preferred. The transition metals include titanium, zirconium, hafnium, thorium, uranium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten and manganese, with titanium, zirconium, and vanadium as the preferred metal components since they are the most active of the above metals. Titanium tetrachloride and titanium trichloride are preferred for use in the present invention. Preformed catalyst components can also be used, such as, for example, partially reduced heavy transition metal compounds alone or cocrystallized with a Group II or III metal halide, e.g., aluminum chloride, boron trichloride, zinc chloride and the like.

The organo-metallic compounds of metals of the A subgroup of Groups I and II of the Periodic Table useful in the present invention include the alkyl, cycloalkyl, aralkyl and aryl derivatives. Alkyl lithium compounds having from 2 to 20 carbon atoms per alkyl group, such as isopropyl lithium, and alkyl beryllium compounds having from 2 to 20 carbon atoms per alkyl group, such as diethyl beryllium, are particularly preferred for use erein.

The catalyst is prepared by contacting the transition metal halide with the organo-metallic compound in an inert diluent and in a non-oxidizing atmosphere with stirring.

The process of the invention is carried out by contacting the cis form of at least one (2 43 Type II olefin in a temperature of from -50 to 200 C., preferably 10 to wt. percent. The reaction time is not critical and generally periods of time ranging from 0.5 to 2 hours are suitable in batch runs. The process can also be run continuously if desired. The catalyst slurry is preferably diluted with additional solvent to provide a catalyst conpolymer has been obtained, a C to C alkanol such as isopropyl alcohol or n-butyl alcohol, desirably in combination with a chelating agent such as acetylacetone or carbons are n-heptane, n-hexane, n-decane, neopentane, isoheptane, etc. Examples of aromatic diluents are benzene, toluene, xylene, mesitylene, pseudocu'mene, ethylbenzene, cymene, tetralin, decalin, chlorobenzene, o-dichlorobenzene, orthochlorotoluene and the like.

.Polymers, prepared in accordance with the present invention are generally viscous oily polymers having a which does not polymerize to any appreciable extent. by the process of the invention.

Example 6 Substantially equal molar amounts of cis 2-butene and viscosit average molecular weight of at least 400 and are 5 useful ai s viscosity index improvers in lubricating oils, or Q P are n u d Into a solution of 18011113133 1 can be used themselves as lubricating oils. Additionally, hthhlm and vahadluhl tetrachlqnfile m 1 mar i to Ilene the polymers can be sulfonated or sulfated to give a high The h f who lsopropyll i i h g quality detergent. Also, the polymers containing sufficient chlonde 15 about The ymenzatlon.lsdcorfl g a unsaturation are useful for the alkylation of benezene 1O fltemperalufa of about C- fOr a perlo 0 our;

which, when followed by sulfonation of the resulting prodhe'reshhlhg Polymer obtalned afier fii'tratlon and i uct, yields a completely oil soluble detergent. Also, by 15 n V a ia having a v1scos1ty average rno ecutilizing conventional oxidation and sulfonation proce- Welght of about dures high molecular weight alcohols, carboxylic acids Example 7 ,i g gigggi can be prepared from the Polymers of 15 An equal molar mixture of cis Z-pentene and cis lhen l-Z-butene is introduced into a solution of diethyl- The mvenhon will be betthr under.stoodf byurefereI-lce heryl lium and TiCl .O.33AlCl in 2 liters of n-heptane. to the followmg 18mphs Whlch are F 1 The molar ratio of diethylberyllium to TiCl .O.33AlCl is Purposes only and are not meant to hmlt t e mventlon' 20 about 2:1. The polymerization is conducted at a tempera- Example 1 ture of about 90 C. for a period of about 45 minutes. lsopropyl lithium, 20 mmoles in nheptzme was added The resulting polymer obtained after filtration and washto a Solution of 10 mmoles of Tick in 500 mL of mg 15 an oily substance having a VlSCOSl'tY average molectane..Cis 2-butenewas added to the catalyst suspended in 111? }g o about 600. v n-heptane continuously during the polymerization, at the the Present Process cahbe fi i out rate of 1100 cc./ min. The polymerization was carried out Without departing from the Scope and Spmt of t e mven' at 50 C. for 51 minutes. The resulting oily polymer was 7 isolated by treating the cooled reaction mixture with 20 What clalmed ml. of acetone, followed by 200 ml. of 6 N hydrochloric A Q F for tha Polymenzanon of C15 Type H acid. The organic layer was dried over anhydrous MgSO compnsmg contacting at least one q i conslst and then subjected to distillation. 17.3 gms. of oily P lymer 53 1 222; g g gg g g g g ii g fi :22: were obtained with an average molecular weight of 415. hydrocarbon diluent at temperatures of about to Example 2 200 C. and at pressures ranging from atmospheric to 30 Cis Z-butene was bubbled, at the rate of 1100 cc./min. atmSPheYeS, With a at lyst consisting essentially of a into 200 of whemane containing 83 mmoles of BeEt2 reducible halide of a transltlon metal of Group VIII and and 3.'5 mmoles of TiCl The polymerization was carthe A subgroup of Groups IV to V1 actuated Wlth from ried out at 50 C. for 30 minutes. 16.5 gms. of polymer about to 5 moles of h h neta1hc c mPOund having an average molecular weight of 425 were obtained. lected the group cohslshhg' and 40 alkylberylhum per mole of sard halide, thereby forming Example 3 a polymer of said cis isomer having a viscosity average cis Lbutene was polymerized according to the process molecular weight of at least 400, and recovering said of Example 1 using the quantities of ingredients and P y polymerization conditions. shown in Table I. 23.7 gms. of The Process of claim 1 wherein the Catalyst is an oily polymer were obtained alkyllithium-titanium halide catalyst.

E l 4 3. The process of claim 1 wherein the catalyst is a xamp e dialkylberyllium-titanium halide catalyst.

In order to demonstrate the applicability of the instant 4. The process .of claim 1 wherein the monomer is cis process to the cis isomers only, a run similar to that of Z-butene.

Example 3 was carried out using trans Z-butene. Details 5. The process of claim 1 wherein the polymerization are also giveninTable 1. temperature is from 10 to 90 C. and the diluent is an aliphatic hydrocarbon diluent.

Examp 1e 5 6. A process for the polymerization of cis Type II The process of Example 1 was carried out using 140, olefins comprising contacting a monomer consisting solely gms. of Z-heptene as the olefin. The 2-heptene was an of a C to C Type II olefin containing at least about 50 equimolar mixture of the cis and trans isomers. Details of wt. percent of the cis isomer of said olefin, in an inert this polymerization reaction are also given in Table I. hydrocarbon diluent at a temperature of about -50 to TABLE I Example Monomer i-PrLi TiCh Li/Ti T emp. Heptane Oily Polymer (mmoles) (mmoles) 0.) (ml) (g) 3 Cis 2-hutene 13.2 13.2 1 58 600 23.7 4 Trans 2-butene 13.2 13.2 1 60 600 1.2 5 Z-heptene 14.3 13. 2 1.1 71 500 5.2

1 The 2-heptene used was a mixture of the cis and trans isomer.

It can be seen from the above table that the polymeriza- 200 C. and at pressures ranging from atmospheric up to tion of cis Z-butene gives a satisfactory yield of 23.7 gms. 30 atmospheres, with a catalyst consisting essentially of a of oily polymer. However, trans 2-butene gave a yield of titanium halide activated with from about 0.5 to 5 moles only 1.2 grams of polymer. The 2-heptene run (Example of an alkyl metallic compound selected from the group 5) gavea yield of 5.2 grams of oily polymer. The relaconsisting of diethylberyllium and isopropyl lithium per tively lower yield of polymer from this run compared to mole of said titanium halide, thereby forming a polymer the cis Z-butene run of Example 3 is undoubtedly due to of said cis isomer having a viscosity average molecular the fact that one-half of the monomer is the trans isomer 75 weight of at least 400, and recovering said polymer.

7. A process comprising the steps of polymerizing a monomer consisting solely of cis Z-butene in an inert hydrocarbon diluent at temperatures of about 50 to 200 C. and at pressures ranging from atmospheric to 100 atmospheres using as a catalyst titanium tetrachloride activated with 0.5 to 5 moles of isopropyl lithium per mole of said titanium tetrachloride, and recovering a polymer of said butene.

References Cited UNITED STATES PATENTS 11/1962 Strohmayer et a1. 26093.7

FOREIGN PATENTS 12/1955 Belgium.

3/1959 Great Britain. 11/ 1959 Great Britain.

PAUL M. COUGHLAN, JR., Primary Examiner.

ALPHONSO D. SULLIVAN, Examiner. 2,832,759 4/1958 Nowlm et al 26093.5 

1. A PROCESS FOR THE POLYMERIZATION OF CIS TYPE II OLEFINS COMPRISING CONTACTING AT LEAST ONE MONOMER CONSISTING SOLELY OF A C4 TO C12 TYPE II OLEFIN CONTAINING AT LEAST 50 WT. PERCENT OF THE CIS ISOMER OF SAID OLEN, IN AN INERT HYDROCARBON DILUENT AT TEMPERATURE OF ABOUT -50 TO 200*C. AND AT PRESSURES RANGING FROM ATMOSPHERIC TO 30 ATMOSPHERES, WITH A CATALYST CONSISTING ESSENTIALLY OF A REDUCIBLE HALIDE OF A TRANSITION METAL OF GROUP VIII AND THE A SUBGROUP OF GROUPS IV AND VI ACTIVATED WITH FROM ABOUT 0.5 TO 5 MOLES OF AN ALKYL METALLIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALKYL-LITHIUM AND DIALKYLBERYLLIUM PER MOLE OF SAID HALIDE, THEREBY FORMING A POLYMER OF SAID CIS ISOMER HAVING A VISCOSITY AVERAGE MOLECULAR WEIGHT OF AT LEAST 400, AND RECOVERING SAID POLYMER. 